Hydrogenation of solid carbonaceous materials using mixed catalysts

ABSTRACT

This invention encompasses systems and methods for converting solid carbonaceous material to a liquid product, comprising maintaining a solid carbonaceous material in the presence of at least one active source of zinc at a reaction temperature of greater than 350° C. and at a pressure in the range of 300 to 5000 psig for a time sufficient to form a liquid product.

TECHNICAL FIELD

This invention relates to systems and processes for pretreating acarbonaceous material, for liquefying a carbonaceous material, and forimproving efficiency of carbonaceous material liquefaction.

BACKGROUND

Much work has been done over the years on processes for obtaining liquidand gaseous products from solid carbonaceous materials such as coal. Theknown processes include both catalytic and non-catalytic reactions. Incatalytic processes, the hydrocarbonaceous material is typicallyslurried with a solvent and a catalyst, and is reacted in the presenceof molecular hydrogen at elevated temperatures and pressures.

U.S. Pat. No. 5,246,570, for example, describes a coal liquefactionprocess in which a mixture of coal, catalyst, and solvent are rapidlyheated to a temperature of 600-750° F. in a preheater, and then reactedunder coal liquefaction conditions in a liquefaction reaction. U.S. Pat.No. 5,573,556 describes a process for converting a carbonaceous materialto normally liquid products comprising heating a slurry that comprises acarbonaceous material, a hydrocarbonaceous solvent, and a catalystprecursor to a temperature sufficient to convert the catalyst precursorto the corresponding catalyst, and introducing the slurry into aliquefaction zone. U.S. Pat. No. 5,783,065 describes a coal liquefactionprocess comprising impregnating coal particles with a catalyst havinghydrogenation or hydrogenolysis activity; introducing the impregnatedcoal particles for very short periods into a turbulent flow of hydrogencontaining gas at a temperature at least about 400° C.; and quenchingthe temperature of the products to a temperature significantly less than400° C.

Such conventional processes leave much room for improving the liquidand/or gas yields of hydroconverted carbonaceous materials, as well asthe quality of the liquid and/or gas products that are obtained fromsuch processes. Accordingly, a need remains for improved systems andprocesses for hydroconversion of carbonaceous materials, as well asimproved feed materials for such systems and processes.

SUMMARY OF THE INVENTION

The present invention relates to a process for converting solidcarbonaceous material to a liquid product, comprising maintaining asolid carbonaceous material in the presence of at least one activesource of zinc and at least one active source of a second metal at areaction temperature of greater than 350° C. and at a pressure in therange of 300 to 5000 psig for a time sufficient to form a liquidproduct.

In one aspect, the process comprises preparing a combination of thesolid carbonaceous material, at least one hydrocarbonaceous liquid, atleast one active source of zinc and at least one active source of thesecond metal; and passing the combination to a hydroconversion reactionzone and maintaining the solid carbonaceous material at a reactiontemperature of greater than 350° C. and at a pressure in the range of300 to 5000 psig for a time sufficient to convert at least a portion ofthe solid carbonaceous material to a liquid product boiling in thetemperature range of C₅ to 650° C.

In a further aspect, the step of preparing the combination comprisespreparing a mixture comprising at least one active source of zinc and atleast one active source of a second metal; combining the mixture withcoal to form catalyst-containing coal particles; providing ahydrocarbonaceous liquid to the catalyst-containing coal particles toprepare the combination.

In another aspect, the process of preparing the combination furthercomprises drying the catalyst-containing coal prior to the step ofpassing the combination to the hydroconversion reaction zone.

In a further aspect, the process further comprises pretreating thecombination at a pretreatment temperature within the range of 100-350°C. and for a time of between 5 and 600 minutes prior to passing thecombination to the hydroconversion reaction zone.

In a further aspect, before, during or after the step of pretreatment,at least one active source of sulfur is added to the solid carbonaceousmaterial in the preparation of the combination, wherein the atomic ratioof sulfur to metal components is within the range of between 1/1 and10/1.

In an aspect, the second metal is iron.

Several embodiments of the invention, including the above aspects of theinvention, are described in further detail as follows. Generally, eachof these aspects can be used in various and specific combinations, andwith other aspects and embodiments unless otherwise stated herein.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1, FIG. 2, FIG. 3 and FIG. 4 illustrate embodiments of the processfor converting solid carbonaceous material.

DETAILED DESCRIPTION

The following terms will be used throughout the specification and willhave the following meanings unless otherwise indicated.

The term “catalyst precursor” is used herein to refer to a compound thatis transformable into a catalyst via chemical reaction with one or morereagents (such as sulfiding and/or reducing agents, e.g., hydrogen, suchas within a hydrocarbon medium) and/or via any other suitable treatment(such as thermal treatment, multi-step thermal treatment, pressuretreatment, or any combination thereof) whereby the catalyst precursor atleast partially decomposes into a catalyst.

The term “active source” is used herein to refer to an atomic,molecular, complex or any other form of an element that is a catalyst ora catalyst precursor or that can be converted into a catalyst orcatalyst precursor. The active source may be in solution, in slurry orin particle form. When the active source is deposited on the solidcarbonaceous material, by, for example, plating, impregnation, coatingor washing, a single active source or a mixture of active sources may bedeposited on individual particles of the solid carbonaceous material.

The term “catalytic material” is used to refer to one or more activecatalysts or catalyst precursors. The component(s) of catalytic materialmay be in slurry or particle form. In particle form, single or multiplecatalysts may be present on individual particles. Likewise, when thecatalytic material is deposited on the solid carbonaceous material, by,for example, plating, impregnation, coating or washing, a singlecatalyst, or a mixture of catalysts or precursors making up thecatalytic material may be deposited on individual particles of the solidcarbonaceous material.

Unless otherwise specified, coal properties as disclosed herein are on adry, ash-free (daf) basis, wherein ASTM 3173 is used for moisturedetermination and ASTM3174 for ash quantification.

“d” block elements refer to elements of the Period Table wherein the dsublevel of the atom is being filled. Examples include iron, molybdenum,nickel, manganese, vanadium, tungsten, cobalt, copper, titanium,chromium, platinum, palladium, cerium, zirconium, zinc and tin.

Lanthanoid (or lanthanide, or sometimes referred to as rare earths)elements refer to the fifteen elements in the Periodic Table with atomicnumbers 57 through 71.

“Oil dispersible” compound means that the compound scatters or dispersesin oil forming a dispersion. In one embodiment, the oil dispersiblecompound is oil soluble which dissolves upon being mixed with oil.

For purposes of this disclosure, unless otherwise specified, thecatalyst composition is defined as the composition of the activesource(s) added to the process, regardless of the form of the catalyticelements during hydroconversion.

The present invention relates to the composition and preparationprocedures of a sulfided zinc-containing catalyst used forhydroconversion of carbonaceous material including coal, shale oil,vacuum residuum and bio-fuel stock such as lignin. The invention furtherrelates to a hydroconversion process for converting solid carbonaceousmaterial to a liquid product in the presence of a catalyst compositioncomprising zinc. In embodiments, the invention further relates to aprocess for converting a carbonaceous material, comprising pretreating asolid carbonaceous material at a pretreatment temperature and in thepresence of at least one active source of zinc and at least one activesource of a second metal; heating the pretreated material in thepresence of hydrogen to a conversion temperature which is greater thanthe pretreatment temperature; and reacting the heated material for atime sufficient to form converted products from the solid carbonaceousmaterial.

Catalyst Formula

In one embodiment, the catalyst composition as expressed in elementalform is of the general formula(R^(p))_(i)(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h).The formula herein refers to the catalyst solids, constituting thecatalyst slurry in oil. In the equation, M and L each represents atleast a “d” block element from the Periodic Table such as iron,molybdenum, nickel, manganese, vanadium, tungsten, cobalt, copper,titanium, chromium, platinum, palladium, cerium, zirconium, zinc andtin. M is different from L. R is optional, which represents at least onelanthanoid element from the Periodic Table such as La, Ce, Nd, etc. Inanother embodiment, R is at least an alkali earth metal such asmagnesium.

Also in the equation, p, t, u, v, w, x, y, z representing the totalcharge for each of the components (R, M, L, S, C, H, O and N,respectively); pi+ta+ub+vd+we+xf+yg+zh=0; R with a subscript i rangingfrom 0 to 1; M and L with subscripts a and b, with values of a and brespectively ranging from 0 to 5, and (0<=b/a<=5); S represents sulfurwith the value of the subscript d ranging from 0.5(a+b) to 5(a+b); Crepresents carbon with subscript e having a value of 0 to 11(a+b); H ishydrogen with the value off ranging from 0 to 7(a+b); O representsoxygen with the value of g ranging from 0 to 5(a+b); and N representsnitrogen with h having a value of 0 to 2(a+b).

In embodiments, M is iron and L is zinc (or vice versa). In some suchembodiments, the catalyst is of the formula(Fe_(z)Zn_(1-z))_(a)(S)_(d)(C)_(e)(H)_(f)(O)_(g)(N)_(h), wherein thezinc to iron ratio is in the range of 9:1-1:9 (as wt. %). In some suchembodiments, the zinc to iron ratio is in the range of 1:5 to 5:1; or inthe range of 1:10 to 1:5.

Pretreatment Process

In embodiments, the present invention is related to a system and processfor pretreating a carbonaceous material, for dispersing one or morecatalysts or catalyst precursors into a carbonaceous material, forenhancing the conversion of a carbonaceous material (such as anaturally-occurring solid carbonaceous material, such as coal) to aliquid and/or gaseous product, for producing a carbonaceous material ofenhanced reactivity, for improving efficiency of carbonaceous material(such as coal) liquefaction, as measured for example by conversion andliquid yield, and/or for lowering hydrogen consumption duringliquefaction of carbonaceous material.

In one embodiment, such pretreating of a carbonaceous material isperformed or accomplished using reaction conditions (or a combination ofconditions, such as temperature, pressure, and/or duration ofpretreatment) at which substantially no hydroconversion of thecarbonaceous material occurs (i.e., wherein less than about 20%, lessthan about 10% or even less than about 1% of the carbonaceous materialis converted) during the pretreatment step. Any suitable process oroperating conditions can be utilized to pretreat the carbonaceousmaterial. In one embodiment, the pretreatment composition is heated to atemperature sufficient to cause one or more catalysts or catalystprecursors to disperse into the carbonaceous material, and ismaintained, held, and/or kept at this pretreatment temperature for atime or duration sufficient to disperse one or more of the catalysts orcatalyst precursors into the carbonaceous material to a desired degreeof dispersion, integration, and/or homogeneity. In one embodiment, thepretreatment composition is heated to a temperature of about 100-350° C.(such as about 150-300° C. or even about 180-220° C.). In some suchembodiments, the step of pretreating is conducted at a temperature ofabout 100-350° C. for about 10-360 minutes.

The pretreatment composition is preferably maintained, kept, and/or heldat the pretreatment temperature for a time or duration sufficient tocause swelling of the carbonaceous material and to allow for dispersion(such as complete dispersion and/or homogenous dispersion) of thecatalyst or catalyst precursor into the carbonaceous material. In oneembodiment, for example, the pretreatment composition is maintained,kept, and/or held at suitable temperature for a suitable duration tocause the total volume of voids of the carbonaceous material (or of eachparticle of carbonaceous material) to increase by greater than about 5%,or about 25% as compared to the carbonaceous material prior topretreatment. In one embodiment, in this regard, the pretreatmentcomposition is maintained at the pretreatment temperature for a time ofbetween 5 and 600 minutes, or between 10 and 360 minutes.

Pretreatment of the carbonaceous material can be performed under anysuitable atmosphere. In one embodiment, the pretreatment of carbonaceousmaterial occurs under an inert atmosphere. In another embodiment, thepretreatment occurs under a reducing atmosphere, such as under hydrogenand/or a synthesis gas (“syn-gas”) pressure. In some embodiments, forexample, the pretreatment is performed at a pressure between atmosphericpressure and about 500 psig, e.g., a pressure of about 100-450 psig, orabout 200-350 psig. In other embodiments, the pretreatment occurs undera reducing atmosphere at a pressure defined by the hydroconversionprocess, such as at a pressure of about 300-5000 psig, such as 500-3500psig, about 1000-3000 psig, or even about 1500-2600 psig. Any suitablesyn-gas can be used in this regard, such as, for example, a syn-gas thatcomprises a 1:1 to 2:1 mixture of hydrogen with carbon monoxide, andoptionally also contains carbon dioxide, methane, and/or othercomponents.

In one embodiment, such pretreatment is performed or accomplished underconditions sufficient to deposit at least a portion of the catalyst orcatalyst precursor onto the solid carbonaceous material duringpretreatment. In some such embodiments, one or more catalysts orcatalyst precursors and a liquid contact the solid carbonaceousmaterial.

The pretreatment composition comprising the carbonaceous material, oneor more catalyst or catalyst precursors, and a hydrocarbonaceous liquidcan be prepared in any suitable manner. In one embodiment, thecarbonaceous material, catalyst or catalyst precursor, andhydrocarbonaceous liquid are simply mixed to form a pretreatmentcomposition, and the pretreatment composition is subjected topretreatment conditions. In another embodiment, the carbonaceousmaterial is contacted with the catalyst or catalyst precursor in thepresence of the hydrocarbonaceous liquid, and the pretreatmentcomposition is subjected to pretreatment conditions. In anotherembodiment, the carbonaceous material is ground in the presence of theone or more catalysts or catalyst precursors and the hydrocarbonaceousliquid, to produce a pretreatment composition in the form of a slurry;and the pretreatment composition is subjected to pretreatmentconditions. In another embodiment, the carbonaceous material is groundin the presence of the hydrocarbonaceous liquid to produce a slurry; theone or more catalyst precursors are added to the slurry to form apretreatment composition; and the pretreatment composition is subjectedto pretreatment conditions. In other embodiment, the catalyst orcatalyst precursor is added at the start of the pretreatment process. Inanother embodiment, the catalyst or catalyst precursor is added atintervals throughout a pretreatment process. In other embodiments, atleast a portion of the catalyst or catalyst precursor is deposited onthe carbonaceous material during pretreatment.

Following pretreatment of the carbonaceous material, the carbonaceousmaterial and dispersed catalyst or catalyst precursor, optionallytogether with the hydrocarbonaceous liquid, form an improved feed for ahydroconversion process. Such an improved feed can be used for anysuitable hydroconversion process to produce a liquid and/or gaseousproduct.

Carbonaceous Material

The carbonaceous material can be any suitable solid carbon containingmaterial, such as any naturally occurring solid, or normally solid,carbon containing material. Specifically, for example, the carbonaceousmaterial can be coal, such as anthracite, bituminous coal,sub-bituminous coal, lignite, or any combination or mixture thereof. Thecarbonaceous material can also be any heteroatom-containing solidcarbonaceous material or feed, as well as any heavy hydrocarbonaceousfeeds, such as, for example, coal, coke, peat, shale oil and/or asimilar material, such as any solid carbonaceous material containing arelatively high ratio of carbon to hydrogen, or combinations or mixturesthereof. In some embodiments, at least a portion of the carbonaceousmaterial is in the form of particles, or finely divided particles,having any suitable size. For example, at least about 50 wt % of thecarbonaceous material is in the form of particles having a mean particlediameter of less than about 0.5 inches. In embodiments, at least greaterthan 70 wt % of carbonaceous material is in the form of particles havinga mean particle diameter in the range of about 0.1 to 0.4 inches. In oneembodiment, greater than about 80 wt. % of the carbonaceous material isin the form of particles having a mean diameter less than about 0.25inches. In another embodiment, greater than 80 wt % of the carbonaceousmaterial is in the form of particles having a mean diameter in the rangeof 50 microns to 500 microns, such as 100 microns. Such particles can beformed in any suitable manner, such as by grinding at least a portion ofthe carbonaceous material. In one embodiment, at least a portion of thecarbonaceous material is ground in the presence of one or more catalystsor catalyst precursors and the hydrocarbonaceous liquid. In anotherembodiment, at least a portion of the carbonaceous material is ground inthe presence of the hydrocarbonaceous liquid to form a slurry, and (suchas subsequently) mixing the slurry with one or more catalysts orcatalyst precursors. In other embodiments, the carbonaceous material isground under an inert or a reducing atmosphere, such as, for example,hydrogen, nitrogen, helium, argon, syn-gas, or any combination ormixture thereof. Any process or equipment may be used to grind thecarbonaceous material, such as, for example, a hammer mill, a ball mill(such as a wet ball mill, a conical ball mill, a rubber roller mill), arod mill, or a combination thereof.

Hydrocarbonaceous Liquid

The hydrocarbonaceous liquid can be any suitable liquid (such as solventor diluent) known in the art to be useful for the liquefaction ofcarbonaceous materials (such as solid carbonaceous materials, such ascoal). In one embodiment, the hydrocarbonaceous liquid is a hydrogendonor solvent, such as any compound(s) which functions as a hydrogendonor in hydroconversion conditions. The hydrocarbonaceous liquid canhave any suitable hydrogen donatability, such as, for example, ahydrogen donatability greater than about 1.0 wt %, as determined, forexample, by NMR.

In one embodiment, the hydrocarbonaceous liquid comprises a coal-derivedsolvent, or a distillate fraction thereof. In another embodiment, thehydrocarbonaceous liquid comprises a hydrogenated aromatic, a naphthenichydrocarbon, a phenolic material, or a similar compound, or acombination or mixture thereof. In another embodiment, thehydrocarbonaceous liquid comprises one or more aromatics, such as one ormore alkyl substituted aromatics. Solvents known to donate hydrogenduring liquefaction include, for example, the dihydronaphthalenes, theC₁₀-C₁₂ tetrahydronaphthalenes, the hexahydrofluorenes, the dihydro-,tetrahydro-, hexahydro- and octahydrophenanthrenes, the C₁₂-C₁₃acenaphthenes, the tetrahydro-, hexahydro- and decahydropyrenes, thedi-, tetra- and octahydroanthracenes, and other derivatives of partiallysaturated aromatic compounds. They can be prepared by subjecting adistillate stream from atmospheric distillation to a conventionalhydrogenation reactor. Particularly effective mixed solvents includeheavy gas oil fractions (often called vacuum gas oils, or VGO) with aninitial boiling point of about 343° C. (650° F.) and a final boilingpoint of about 538° C. (1000° F.). This stream comprises aromatics,hydrogenated aromatics, naphthenic hydrocarbons, phenolic materials, andsimilar compounds. If a solvent is used which does not have donatablehydrogen, hydrogen may be added from another source.

The solvent generally boils at a temperature greater than 300° C., suchas, for example a temperature in the range of 450-900 or 650-850° F. Inone embodiment, the hydrocarbonaceous liquid is a fluid catalyticcracking (FCC) type process oil cut that boils at a temperature of about500° F. or higher (FCC-type process oil (500° F.+cut)). In anotherembodiment, the hydrocarbonaceous liquid is an FCC-type process oilboiling at a temperature of about 500° F. or less (“FCC-type process oil(500° F.−cut)”). In another embodiment, the hydrocarbonaceous liquid isa hydrotreated FCC oil. In another embodiment, the hydrocarbonaceousliquid is tetralin (1,2,3,4 tetrahydronaphthalene). In anotherembodiment, the hydrocarbonaceous liquid comprises one or more compoundsthat have an atmospheric boiling point ranging from about 350-850° F.

Any suitable ratio of hydrocarbonaceous liquid to carbonaceous material(such as carbonaceous particles, or even coal particles) can be used inthe context of the present invention, such as, for example, a ratio in arange of about 1:10 to about 10:1, such as 1:6 to about 6:1, or a rangeof about 1:2 to about 2:1, by weight of the mixture. In one embodiment,the ratio of hydrocarbonaceous liquid to carbonaceous material used inthe pretreatment process is about 0.75:1 to about 1:1.

Catalyst Precursor

The process for converting a solid carbonaceous material comprisesheating the carbonaceous material in the presence of a catalystcomposition. In embodiments, the process for converting a solidcarbonaceous material comprises heating a solid carbonaceous material inthe presence of at least one active source of zinc for a time sufficientto form a liquid product from the solid carbonaceous material. Inembodiments, the active source of zinc is provided to the carbonaceousmaterial is the form of a catalyst precursor that is transformable intoa catalyst via chemical reaction with one or more reagents and/or viaany other suitable treatment. The catalyst precursor may be oil soluble,oil dispersible, water soluble and/or water dispersible. In embodiments,the process comprises pretreating the solid carbonaceous material at apretreatment temperature and in the presence of at least one activesource of zinc; heating the pretreated material in the presence ofhydrogen to a conversion temperature which is greater than thepretreatment temperature; and reacting the heated material for a timesufficient to form a liquid product from the solid carbonaceousmaterial.

Suitable catalyst precursors include:

-   -   a) zinc metal;    -   b) zinc containing inorganic compounds, such as the sulfates,        nitrates, carbonates, sulfides, oxysulfides, oxides and hydrated        oxides, ammonium salts and heteropoly acids of zinc;    -   c) salts of organic acids, such as acyclic and alicyclic        aliphatic, carboxylic acids containing two or more carbon atoms        (non-limiting examples include acetates, oxylates, citrates);    -   d) zinc-containing organometallic compounds including chelates        such as 1,3-diketones, ethylene diamine, ethylene diamine        tetraacetic acid, phthalocyanines, thiocarbamates,        phosphorothioates, and combinations or mixtures thereof        (non-limiting examples include zinc alkyl dithiocarbamate, zinc        alkyl phosphorodithioate); and/or,    -   e) zinc salts of organic amines such as aliphatic amines,        aromatic amines, quaternary ammonium compounds, or combinations        or mixtures thereof, and    -   f) zinc-containing minerals.

In embodiments, the process for converting a solid carbonaceous materialfurther comprises heating the solid carbonaceous material in thepresence of at least one active source of a second metal. Inembodiments, the second metal is selected from the group consisting ofiron, molybdenum, tungsten, nickel, cobalt, titanium and tin. In somesuch embodiments, the active source of the metal is provided to thecarbonaceous material is the form of a catalyst precursor that istransformable into a catalyst via chemical reaction with one or morereagents and/or via any other suitable treatment. The catalyst precursormay be oil soluble, oil dispersible, water soluble and/or waterdispersible.

In embodiments, the catalyst composition comprises for converting thesolid carbonaceous material further comprises at least one active sourceof iron. Suitable catalyst precursors which provide the active ironsource include:

-   -   a) iron metal;    -   b) iron containing inorganic compounds, such as the sulfates,        nitrates, carbonates, sulfides, oxysulfides, oxides and hydrated        oxides, ammonium salts and heteropoly acids of iron;    -   c) salts of organic acids, such as acyclic and alicyclic        aliphatic, carboxylic acids containing two or more carbon atoms        (non-limiting examples include acetates, oxylates, citrates);    -   d) iron-containing organometallic compounds including ferrocene,        chelates such as 1,3-diketones, ethylene diamine, ethylene        diamine tetraacetic acid, phthalocyanines, thiocarbamates,        phosphorothioates, and combinations or mixtures thereof        (non-limiting examples include iron alkyl dithiocarbamate, iron        alkyl phosphorodithioate); and/or,    -   e) iron salts of organic amines such as aliphatic amines,        aromatic amines, quaternary ammonium compounds, or combinations        or mixtures thereof, and    -   f) iron-containing minerals.

The catalyst precursor can be formed in any suitable manner prior to thehydroconversion process. In one embodiment, for example, one or morecatalyst precursors are formed by:

-   -   a) mixing a hydrocarbonaceous liquid (such as a liquefaction        solvent) with an active source of at least one metal (such as a        metal oxide, e.g., iron oxide, or other compound containing any        suitable metal as discussed herein) to form a catalyst        precursor,    -   b) combining the catalyst precursor with a carbonaceous        material;    -   c) optionally subjecting the mixture to pretreatment conditions        (such as under hydrogen pressure) in a manner such that one or        more catalyst precursors form in or on the carbonaceous        material; and    -   d) heating the mixture for a time sufficient to form a liquid        product

In embodiments, the catalyst precursors are formed by:

-   -   a) mixing a hydrocarbonaceous liquid (such as a liquefaction        solvent) with at least one active source of zinc and with at        least one active source of a second metal to form a catalyst        precursor;    -   b) combining the catalyst precursor with a carbonaceous        material;    -   c) optionally subjecting the mixture to pretreatment conditions        in a manner such that one or more catalyst precursors form in or        on the carbonaceous material; and    -   d) heating the mixture for a time sufficient to form a liquid        product

In embodiments, the catalyst precursors are formed by

-   -   a) mixing a hydrocarbonaceous liquid with an active source of at        least one metal,    -   b) combining the mixture with a sulfiding agent (such as by        passing hydrogen sulfide through the mixture or adding elemental        sulfur to the mixture) in a manner such that the sulfided        metal-containing compound is dispersible,    -   c) combining the sulfided mixture with a carbonaceous material,    -   d) optionally subjecting the mixture to pretreatment conditions        in a manner such that one or more catalyst precursors form in or        on the carbonaceous material; and    -   e) heating the mixture for a time sufficient to form a liquid        product.

In embodiments, the catalyst precursors are formed by

-   -   a) mixing a hydrocarbonaceous liquid with an active source of at        least one metal;    -   b) combining the catalyst precursor with a carbonaceous        material;    -   c) combining the mixture with a sulfiding agent;    -   d) optionally subjecting the mixture to pretreatment conditions        in a manner such that one or more catalyst precursors form in or        on the carbonaceous material; and    -   e) heating the mixture for a time sufficient to form a liquid        product.

In another embodiment, one or more catalyst precursors are formed by

-   -   a) mixing one or more metal containing compounds, a sulfiding        agent, and water, to form a colloidal suspension,    -   b) combining the colloidal suspension with a hydrocarbonaceous        liquid (such as a liquefaction solvent) to drive water out of        the suspension,    -   c) combining the suspension with a carbonaceous material,    -   d) optionally subjecting the suspension to pretreatment        conditions (such as under hydrogen pressure), in a manner such        that one or more catalyst precursors form in or on the        carbonaceous material; and    -   e) heating the mixture for a time sufficient to form a liquid        product.

In another embodiment, one or more catalyst precursors are by

-   -   a) sulfiding an ammonium containing Group VIB metal compound in        an aqueous phase with hydrogen sulfide, in a substantial absence        of hydrocarbon oil, at a temperature less than about 177° C., to        form a presulfided product; and    -   b) separating ammonia from said presulfided product to form a        sulfided product, in a manner such that one or more catalyst        precursors form in or on the carbonaceous material.

In another embodiment, one or more catalyst precursors are formed by aprocess comprising:

-   -   a) mixing an active source of zinc and an active source of the        second metal and water, to form a colloidal suspension or        solution;    -   b) combining the colloidal suspension or solution with a solid        carbonaceous material at conditions sufficient to deposit at        least a portion of the zinc and a portion of the second metal        onto [wherein depositing onto includes depositing onto the        surface of any fractures, pores, or other openings into the        internal volume of the solid carbonaceous material] the solid        carbonaceous material;    -   c) combining the solid carbonaceous material having the active        sources of the metals deposited thereon with a hydrocarbonaceous        liquid (such as a liquefaction solvent); and    -   d) optionally subjecting the suspension to pretreatment        conditions (such as under hydrogen pressure), in a manner such        that one or more catalyst precursors form in or on the        carbonaceous material; and    -   e) heating the mixture for a time sufficient to form a liquid        product.

In some such embodiments, the process further comprises combining thecolloidal suspension or solution and an active source of sulfur with thesolid carbonaceous material.

Any suitable amount of the catalytic materials can be used tohydroconvert the carbonaceous material in the context of the presentinvention. In one embodiment, the mixture of catalyst precursor,carbonaceous material, and hydrocarbonaceous liquid comprises about25-10000 ppm (such as about 50-9000 ppm, about 100-8000 ppm, about250-5000, about 500-3000 ppm, or even about 1000-2000 ppm) of one ormore catalyst or catalyst precursor by weight, based on the total weightof the mixture. In embodiments, the metal content of the catalyst orcatalyst precursor refers to added metal, and does not include metalwhich is native to the carbonaceous material, or metal which is erodedfrom processing equipment.

The catalytic materials can be used in the context of the presentinvention in any suitable form, such as, but not limited to, particulateform, impregnated within a carbonaceous material, dispersed in thehydrogen donor solvent, and/or soluble in the hydrogen donor solvent.Additionally, the catalytic materials may be used in processes employingfixed, moving, and ebullated beds as well as slurry reactors.

The catalyst precursor(s) can be transformed into a catalyst by thermaldecomposition, such as prior to or during liquefaction, without theaddition of additional reactants. In other embodiments, followingpretreatment, one or more additional reactants can be added to thepretreated carbonaceous material mixture (such as prior to or during theliquefaction process), to transform the dispersed catalyst precursorinto a catalyst. Any suitable reactants can be used in this regard, suchas for example any suitable sulfiding or reducing agents.

Sulfiding Agent Component

In embodiments, the catalyst composition further comprises at least oneactive source of sulfur. In those embodiments in which catalystprecursors are utilized, one or more sulfur compounds can be addedsubsequent to the pretreating step to activate the catalyst precursor toits corresponding sulfided active catalyst. The one or more sulfurcompounds can be introduced at any point of the system, followingpretreatment. In one embodiment, one or more sulfur compounds areintroduced into the pretreatment zone following the performance of thepretreatment process and before the pretreatment composition isdelivered to the liquefaction zone. In another embodiment, one or moresulfur compounds are introduced into the liquefaction zone.

In one embodiment, the catalyst is prepared using a sulfiding agent inthe form of a solution which, under prevailing conditions, isdecomposable into hydrogen sulfide. Such a sulfiding agent can be usedin any suitable amount in preparing the catalyst, such as in an amountin excess of the stoichiometric amount required to form the catalyst. Inone embodiment, the sulfiding agent is present in a sulfur to zinc moleratio of at least 3 to 1. Additionally, any suitable sulfiding agent(such as described above with respect to the catalyst precursor) can beused.

In one embodiment, the sulfiding agent is an aqueous ammonium sulfide.Such a sulfiding agent can be prepared in any suitable manner, such asfrom hydrogen sulfide and ammonia. This synthesized ammonium sulfide isreadily soluble in water and can easily be stored in aqueous solution intanks prior to use.

Suitable sulfiding agents include, for example, any sulfur compound thatis in a readily releasable form, such as, for example, hydrogen sulfide,ammonium sulfide, dimethyldisulfide, ammonium sulfate, carbon disulfide,elemental sulfur, and sulfur-containing hydrocarbons. Elemental sulfuris preferred in some embodiments, because of its low toxicity, low cost,and ease of handling. Additional sulfiding agents include, for example,ammonium sulfide, ammonium polysulfide, ammonium thiosulfate, sodiumthiosulfate, thiourea, dimethyl sulfide, tertiary butyl polysulfide,tertiary nonyl polysulfide, and mixtures thereof. In another embodiment,the sulfiding agent is selected from the group consisting of alkali-and/or alkaline earth metal sulfides, alkali- and/or alkaline earthmetal hydrogen sulfides, and mixtures thereof.

The sulfiding agent can be added in any suitable form. In oneembodiment, elemental sulfur is added to the carbonaceous materialmixture in the form of a sublimed powder or as a concentrated dispersion(such as a commercial flower of sulfur). Allotropic forms of elementalsulfur, such as orthorhomic and monoclinic sulfur, are also suitable foruse herein. In one embodiment, the one or more sulfur compounds are inthe form of a sublimed powder (flowers of sulfur), a molten sulfur, asulfur vapor, or a combination or mixture thereof.

The sulfiding agent can be used in any suitable concentration. In oneembodiment, a concentration of sulfur is introduced such that the atomicratio of sulfur to metal in the catalyst precursor is in the range offrom about 1:1 to about 10:1, such as from about 2:1 to about 8:1, about2:1 to about 7:1, about 2:1 to about 6:1, about 2:1 to about 9:1, about2:1 to about 8:1, about 2:1 to 7:1, about 3:1 to about 9:1, about 3:1 toabout 8:1, about 3:1 to about 7:1 or even about 3:1 to about 6:1.

Catalyst

The catalyst contains an active catalytic component in elemental orcompound form. Examples include finely divided particles, salts, orcompounds of the transition elements, particularly Groups IV-B, V-B,VI-B or Group VIII of the Periodic Table of the Elements, as shown inHandbook of Chemistry and Physics, 45th Edition, Chemical RubberCompany, 1964. In embodiments, alkaline earth elements, such asmagnesium, may be included. In embodiments, lanthanoid (or lanthanide,or sometimes referred to as rare earths) elements refer to the fifteenelements in the Periodic Table with atomic numbers 57 through 71, may beincluded.

The catalyst includes any zinc-containing material that is suitable foruse in a hydroconversion process for a carbonaceous material (such ascoal) when subjected to and/or when experiencing suitable catalyzingreaction conditions. The catalyst further comprises any suitable metal,such as, for example, a metal selected from the group consisting ofGroup IIB metals, Group IIIB metals, Group IVA metals, Group IVB metals,Group VB metals, Group VIB metals, Group VIIB metals, Group VIII metals,or a combination or mixture thereof, such as in combination with one ormore of oxygen, sulfur, nitrogen, and phosphorous. In embodiments, asecond metal is selected from the group consisting of Fe, Mo, W, Co, Ni,Cu, Ti and Sn.

In embodiments, the sulfided zinc-containing catalyst can be ZnS—FeS,ZnS—MoS₂, ZnS—WS₂, ZnS—CoS, ZnS—NiS, ZnS—CuS, ZnS—TiS₂, ZnS—SnS and anyof their combinations and mixtures, for example ZnS—MoS₂—TiS₂. In thecatalyst system, zinc can be the rich phase or serve as dopant.

The amount of zinc that is provided as a catalyst component of thecatalyst is sufficient to catalyze the conversion of the solidcarbonaceous material to liquid hydrocarbons; likewise, the amount ofthe second metal that is provided as a catalyst component is sufficientto catalyze the conversion of the solid carbonaceous material. Inembodiments, zinc is present in the catalyst in an amount of 10 ppm to10 wt %, based on dry, ash free coal. In some such embodiments, zinc ispresent in the catalyst in the amount of 0.1 wt % to 5 wt %. Anexemplary quantity of zinc, as metal, present in the catalyst is in theamount of 0.5 wt % to 2.5 wt %.

In embodiments, the second metal in the catalyst is present in an amountof 10 ppm to 10 wt %, based on dry, ash free coal. In some suchembodiments, the second metal is present in the catalyst in the amountof 0.1 wt % to 5 wt %. An exemplary quantity of the second metal,expressed as a metal, is in the amount of 0.5 wt % to 2.5 wt %. In somesuch embodiments, the second metal in the catalyst is iron. As such,iron is present in the catalyst in an amount of 10 ppm to 10 wt %, basedon dry, ash free coal. In some such embodiments, iron is present in thecatalyst in the amount of 0.1 wt % to 5 wt %. An exemplary quantity ofiron, as metal, present in the catalyst is in the amount of 0.5 wt % to2.5 wt %. In embodiments, the molecular ratio between zinc and othermetals in combination can be between 0.1 to 1 and 10 to 1.

In embodiments, the catalytic materials are added as finely dividedparticulate metal solids, their oxides, sulfides, etc., e.g., FeS_(x);waste fines from metal refining processes, e.g., iron, molybdenum, andnickel; crushed spent catalysts, e.g., spent fluid catalytic crackingfines, hydroprocessing fines, recovered coal ash, and solid coalliquefaction residues. In embodiments, the zinc and the second metal areadded as separate particulate solids. In other embodiments, the catalystcomposition comprises particles that are richer in zinc and leaner inthe amount of the second metal, or particles that are richer in thesecond metal and leaner in the amount of zinc.

In another embodiment, zinc and other metals can form bi-metalliccompounds as a catalyst precursor rather than being added to the feedseparately. As an example, ZnxFe_((1-x))OOH is prepared by titrating aFeSO₄ and ZnSO₄ mixture solution with NH₃H₂O, followed by oxidizing inflowing air at elevated temperatures. Zn_(x)Fe_((1-x))OOH can bepre-sulfided to Zn_(x)Fe_((1-x))S before mixing with the feed.

In embodiments, at least a portion of the catalyst particles areattached to, adsorbed onto, absorbed by, supported on or intimatelyassociated with at least a portion of the solid carbonaceous materialduring conversion of the carbonaceous material. In embodiments, at leasta portion of the catalyst, or catalyst precursor, is deposited on thesolid carbonaceous material before or during pretreatment, using anaqueous or an organic liquid to carry the catalyst or catalyst precursorto the carbonaceous material. In embodiments, at least a portion of thecatalyst, or catalyst precursor, is deposited on the solid carbonaceousmaterial during the step of heating the material to conversiontemperature, or during the conversion process.

In an embodiment, the catalyst is prepared using a catalyst precursorcomprising a metal that comprises a water-soluble zinc component, suchas zinc nitrate, zinc sulfate, zinc acetate, zinc chloride, or a mixturethereof. In another embodiment, the catalyst is prepared using acatalyst precursor comprising an metal that comprises a zinc compoundwhich is at least partly in the solid state, e.g., a water-insolublezinc compound such as zinc carbonate, zinc hydroxide, zinc phosphate,zinc phosphite, zinc formate, zinc sulfide, zinc molybdate, zinctungstate, zinc oxide, zinc alloys such as zinc-molybdenum or zinc-ironalloys, or a mixture thereof. In another embodiment, the catalyst isprepared using a catalyst precursor comprising a metal that comprises awater-soluble zinc sulfate solution which optionally also includes asecond promoter metal compound, such as an iron component in the solutestate selected from iron acetate, chloride, formate, nitrate, sulfate,or a mixture thereof. In one embodiment, the catalyst is prepared usinga catalyst precursor that comprises a metal comprising a zinc sulfateaqueous solution.

In embodiments, at least a portion of the catalyst particles isdispersed as particles separate from the carbonaceous material duringthe pretreatment step, during the step of heating the carbonaceousmaterial to a conversion temperature, or during the conversion process.

In embodiments, the catalyst is dissolved or otherwise suspended in theliquid phase, e.g., as fine particles, emulsified droplets, etc. Thedispersed catalyst can be added to the coal before contact with thehydrocarbonaceous liquid, it can be added to the hydrocarbonaceousliquid before contact with the coal, or it can be added to thecoal-liquid slurry. In some such embodiments, the dispersed catalyst isadded in the form of an oil/aqueous solution emulsion of a water-solublecompound of the catalyst hydrogenation component. The water soluble saltof the catalytic metal can be essentially any water soluble salt ofmetal catalysts. The nitrate or acetate may be the most convenient formof some metals. Non-limiting active sources of zinc include zinc nitrateand zinc acetate. Non-limiting sources of iron are iron nitrate or ironacetate. In embodiments, organometallic complexes such as ferrocene arealso employed as sources of iron. For molybdenum, tungsten or vanadium,a complex salt such as an alkali metal or ammonium molybdate, tungstate,or vanadate may be preferable. Mixtures of two or more metal salts canalso be used. Particular salts are ammonium heptamolybdate tetrahydrate[(NH₄)₆Mo₇O₂₄.4H₂O], nickel dinitrate hexahydrate [Ni(NO₃)₂.6H₂O], andsodium tungstate dihydrate [NaWO₄.2H₂O]. Any convenient process can beused to emulsify the salt solution in the hydrocarbon medium. Thedispersed dissolution catalyst can also be an oil-soluble compoundcontaining a catalytic metal, for example, ferrocene, phosphomolybdicacid, naphthenates of molybdenum, chromium, and vanadium, etc. Suitableoil-soluble compounds can be converted to dissolution catalysts in situ.

In embodiments, the particulate catalyst comprises zinc and a secondmetal as an unsupported catalyst, meaning that the components of thecatalyst are not associated with or supported on inorganic carriers suchas silica, alumina, magnesia, carbon, etc. In other embodiments, atleast a portion of the metal components of the catalyst composition areassociated with or supported on at least one inorganic carrier orbinder. The binder material can comprise any materials that areconventionally utilized as binders in hydroprocessing catalysts.Suitable binder material includes, for example, silica, alumina such as(pseudo) boehmite, silica-alumina compounds, gibbsite, titania,zirconia, cationic clays or anionic clays such as saponite, bentonite,kaoline, sepiolite or hydrotalcite, or combinations or mixtures thereof.In one embodiment, one or more binder materials are selected fromsilica, colloidal silica doped with aluminum, silica-alumina, alumina,titanium, zirconia, or a mixture thereof. In another embodiment, thebinder material comprises a refractory oxide material having at least 50wt. % of titania, on an oxide basis. Any suitable alumina binder can beused in the catalyst preparation process. In one embodiment, the aluminabinder has a surface area ranging from 100 to 400 m2/g, with a porevolume ranging from 0.5 to 1.5 m/g measured by nitrogen adsorption.Similarly, any suitable titania binder can be used in the catalystpreparation process. In one embodiment, the titania of the binder has anaverage particle size of less than 50 microns (such as less than about 5microns) and/or greater than 0.005 microns. In another embodiment, thetitania of the binder has a BET surface area of 10 to 700 m2/g.

In some embodiments, the binder material is a binder that has undergonepeptization. In another embodiment, precursors of the binder materialsare used in the preparation of the catalyst, wherein the precursor isconverted into an effective or functional binder during the catalystpreparation process. Suitable binder material precursors, in thisregard, include alkali metal aluminates (to obtain an alumina binder),water glass (to obtain a silica binder), a mixture of alkali metalaluminates and water glass (to obtain a silica alumina binder), amixture of sources of a di-, tri-, and/or tetravalent metal such as amixture of water-soluble salts of magnesium, aluminum and/or silicon (toprepare a cationic clay and/or anionic clay), chlorohydrol, aluminumsulfate, or a combination or mixture thereof. In the case of supportedcatalysts, the weight ratio of metal components (ie. zinc and the secondmetal components) to support components is in the range of 10:1 to 1:10.

In embodiments, at least a portion of the catalyst particles comprisesadditional components, such as catalyst promoters. Such promoters areselected from the group consisting of a non-noble Group VIII metal (suchas Ni, Co, Fe), a Group VIB metal (such as Cr), a Group IVB metal (suchas Ti), a Group IIB metal (such as Zn), a Group IB metal (such as Cu)and combinations and mixtures thereof.

During the conversion process, during which time the solid carbonaceousmaterial contacted with the active sources of the catalyst compositionand optionally pretreated at a temperature in the range of 100-350° C.and then heated to conversion temperature for conversion of thecarbonaceous material to liquid materials, the active sources of thecatalyst are converted to their active forms. The conversion process isfacilitated by the addition of sulfur to the catalyst.

Properly sulfided zinc species such as ZnS and zinc alkyldithiocarbamate, zinc alkyl phosphorodithioate and sulfided metallicspecies such as MoS₂, ammonium tetrathiomolybdate, NiS, CoS, WS₂, SnS,TiS₂, CuS, FeS, Fe₂S₃, moly alkyl dithiocarbamate, iron alkyldithiocarbamate, titanium alkyl dithiocarbamate, iron alkylphosphorodithioate, can be used directly as catalyst precursors withoutpre-sulfiding. For a non-sulfided metal precursor, including zinc-basedzinc metal, zinc oxide, zinc acetate, zinc nitrate, zinc sulfate andother zinc salts, zinc minerals and zinc organo compounds; iron-basediron metal, iron oxide, ferrous sulfate, ferric nitrate and other ironsalts, red mud and other iron minerals, ferrocene and other iron organocompounds, molybdenum-based, tungsten-based, nickel-based, cobalt-based,titanium-based, copper-based or tin-based metal, oxide, salts, mineralsand organo compounds, etc., elemental sulfur or other sulfiding agentsuch as DMDS, H₂S, CS₂, and (NH₄)₂S can be used to pre-sulfide thecatalyst precursor to form metal sulfides or the sulfiding agent isadded directly during the hydroconversion run to properly sulfide thecatalyst at the atomic ration of (S/(Zn+other metal))=1/1 to 10/1.Alternatively, one or more sulfur compounds can be added during, orsubsequent to the pretreating step to activate the catalyst or catalystprecursor to its corresponding sulfided active catalyst. The one or moresulfur compounds can be introduced at any point of the system. Anysuitable amount of the one or more sulfur compounds can be used in thecontext of the present invention. In one embodiment, one or more sulfurcompounds are introduced into the pretreatment zone following theperformance of the pretreatment process and before the pretreatmentcomposition is delivered to the conversion zone. In another embodiment,one or more sulfur compounds are introduced into the conversion (i.e.liquefaction) zone. In one embodiment, a concentration of sulfur isintroduced such that the atomic ration of sulfur to metal in thecatalyst is from about 2:1 to about 10:1.

Any suitable sulfur compound may be used in this regard. In oneembodiment, the sulfiding agent is hydrogen sulfide (H_(2S)). In oneembodiment, the sulfiding agent is in the form of a solution that underprevailing conditions is decomposable into hydrogen sulfide, present inan amount in excess of the stoichiometric amount required to form thecatalyst. In another embodiment, the sulfiding agent is selected fromthe group of ammonium sulfide, ammonium polysulfide ((NH_(4)2Sx)),ammonium thiosulfate ((NH_(4)2S2O3)), sodium thiosulfate (Na_(2S2O3)),thiourea (CSN_(2H4)), carbon disulfide (CS₂), dimethyl disulfide (DMDS),dimethyl sulfide (DMS), tertiarybutyl polysulfide (PSTB), tertiarynonylpolysulfide (PSTN), and mixtures thereof. In another embodiment, thesulfiding agent is selected from elemental sulfur and sulfur containinghydrocarbons. In another embodiment, the sulfiding agent is selectedfrom alkali- and/or alkaline earth metal sulfides, alkali- and/oralkaline earth metal hydrogen sulfides, and mixtures thereof. The use ofsulfiding agents containing alkali- and/or alkaline earth metals mayrequire an additional separation process step to remove the alkali-and/or alkaline earth metals from the spent catalyst. Elemental sulfurmay be added to the pretreatment composition in the form of a sublimedpowder or as a concentrated dispersion (such as a commercial flower ofsulfur). Allotropic forms of elemental sulfur, such as orthorhombic andmonoclinic sulfur, as also suitable for use herein. In one embodiment,the one or more sulfur compounds are in the form of a sublimed power(flowers of sulfur), a molten sulfur, a sulfur vapor, or a combinationor mixture thereof.

Other Additives

Any additional additives can be utilized during or subsequent to thepretreating step, such as, to enhance or facilitate the pretreatmentprocess (such as by enhancing, facilitating, and/or enhancing dispersionof the catalyst or catalyst precursor into the carbonaceous material)and/or to enhance or facilitate hydroconversion of the pretreatedcarbonaceous material.

Any suitable surfactant can be utilized in the context of the invention,such as to improve dispersion, metal surface area, morphology, and/orother characteristics of the catalyst or catalyst precursor. Suitablesurfactants include, for example, any anionic surfactant, zwitterionicsurfactant, amphoteric surfactant, nonionic surfactant, cationicsurfactant, or combination or mixture thereof. Suitable non-ionicsurfactants include, for example, polyoxyethylenesorbitan monolaurate,polyoxyethylenated alkyphenols, polyoxyethylenated alkyphenolethoxylates, and the like. Suitable cationic surfactants include, forexample, quarternary long-chain organic amine salts, quarternarypolyethoxylated long-chain organic amine salts, and the like, such aswater-soluble cationic amines (e.g., cetyl trimethyl ammonium bromide,cetyl trimethyl ammonium chloride, dodecyl trimethyl ammonium amine,nonyl trimethyl ammonium chloride, dodecyl phenol quaternary aminesoaps, or combinations or mixtures thereof). Suitable anionicsurfactants such as sodium succinate compounds, include, for example,dioctyl sodium sulfosuccinate or sodiumbis(2-ethylhexyl)sulfosuccinate). Suitable surfactants can also comprisesolvent materials having a high surface tension property, such asethylene carbonate; benzophenone; benzyl cyanide; nitrobenzene;2-phenylethanol; 1,3-propanediol; 1,4-butanediol; 1,5-pentanediol;diethyleneglycol; triethyleneglycol; glycerol; dimethyl sulfoxide;N-methyl formamide; N-methylpyrrolidone; and combinations and mixturesthereof. Suitable surfactants also include those surfactants having ahigh surface tension, such as N-methyl pyrrolidone. Other examples ofsurfactants include acetonitrile, acetone, ethyl acetate, hexane,diethyl ether, methanol, ethanol, acetyl acetone, diethylcarbonate,chloroform, methylene chloride, diethyl ketone, and combination andmixtures thereof. In another embodiment, the surfactant comprises anitrogen- or phosphorous-containing organic additive having acarbosulfide phase with enhanced catalytic activities. The amount of theN-containing/P-containing organic additive to be added generally dependson the desired activity of the final catalyst composition.

In another embodiment, the surfactant is an ammonium or phosphonium ofthe formula R₁R₂R₃R₄Q+, wherein Q is nitrogen or phosphorous, wherein atleast one of R₁, R₂, R₃, R₄ is an aryl or alkyl group having 8-36 carbonatoms (e.g., C₁₀H₂₁, C₁₆H₃₃, C₁₈H₃₇, or a combination thereof), andwherein the remainder of R₁, R₂, R₃, R₄ is selected from the groupconsisting of hydrogen, an alkyl group having 1-5 carbon atoms, or acombination thereof. Suitable such examples of surfactants include:cetyltrimethylammonium, cetyltrimethylphosphonium,octadecyltrimethylphosphonium, cetylpyridinium,myristyltrimethylammonium, decyltrimethylammonium,dodecyltrimethylammonium, dimethyldidbdecylammonium, or a combination ormixture thereof. The compound from which the above ammonium orphosphonium ion is derived may be, for example, a hydroxide, halide,silicate, or combination or mixture thereof.

In one embodiment, the surfactant comprises a nitrogen-containingorganic additive, such as aromatic amines, a cyclic aliphatic amines, apolycyclic aliphatic amines, or a combination or mixture thereof. Inanother embodiment, the surfactant comprises a nitrogen-containingorganic additive is selected from compounds containing at least oneprimary, secondary, and/or tertiary amine group (such ashexamethylenediamine, monoethanolamine, diethanolamine, triethanolamine,N,N-dimethyl-N′-ethylethylenediamine, or a combination or mixturethereof); amino alcohols (such as, for example, 2 (2-amino ethylamino)ethanol, 2 (2-aminoethoxy, or a combination or mixture thereof)ethanol, 2-amino-1-butanol, 4-amino-1-butanol, 2,2-diethoxyethylamine,4,4-diethoxybutylamine, 6-amino-1-hexanol, 2-amino-1,3-propanediol,3-amino-1,2-propanediol, 3-amino-1-propanol, or a combination or mixturethereof); and amino alkoxy-silanes (such as, for example,3-glycidoxypropyl) trimethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyl)trimethoxy-silane, or acombination or mixture thereof).

In another embodiment, the surfactant is an organic carboxylic acidsurfactant or stabilizer. In one embodiment, for example, the surfactantis citric acid. In another embodiment, the surfactant is pentadecanoicacid, decanoic acid, or other similar long chain acids. In yet anotherembodiment, the surfactant is alginic acid.

The optional additives can be utilized at any suitable point prior to orafter the pretreatment process and/or hydroconversion process. In oneembodiment, one or more additives are combined with one or more of thecarbonaceous material, hydrocarbonaceous liquid, and one or morecatalysts or catalyst precursors prior to pretreatment. In anotherembodiment, the additive(s) are combined with the carbonaceous material,hydrocarbonaceous liquid, and catalysts or catalyst precursors duringthe pretreatment process. In another embodiment, the additive(s) arecombined with the pretreated carbonaceous material followingpretreatment and before hydroconversion. In yet another embodiment, theadditive(s) are combined with the pretreated carbonaceous materialfollowing during hydroconversion.

The additive(s) can be utilized in any suitable concentration. In oneembodiment, for example, the additive(s) are utilized in a concentrationof about 0.001 to 5 wt. % of the total pretreatment mixture. In anotherembodiment, the additive(s) are utilized in a concentration of about0.005 to 3 wt. % of the total pretreatment mixture. In anotherembodiment, the additive(s) are utilized in a concentration of about0.01 to 2 wt. % of the total pretreatment mixture. If the additive(s)are solely added to the hydroconversion feedstock, the amount to beadded ranges from 0.001 to 0.05 wt. % (such as about 0.005-0.01 wt. %)of the feed, or in any suitable concentration, such as described, forexample, in Acta Petrolei Sinica, Vol. 19, Issue 4, pp. 36-44, ISSN10018719 and in Khimiya I Tekhnologiya Topilv I Masel, Issue 3, Year1997, pp. 20-21, ISSN 00231169, the contents of which are incorporatedherein by reference in their entirety.

Mixing

Any suitable process or system can be used to combine and/or mix thecarbonaceous material with the hydrocarbonaceous liquid and thecatalysts or catalyst precursors. In some embodiments, any suitablemixer is used to simultaneously, successively, and/or sequentially mixthe carbonaceous material, hydrocarbonaceous liquid, and the catalyst orcatalyst precursors in a manner suitable to form a homogenous orheterogeneous mixture (or slurry), as desired. In other embodiments, amixer is utilized in conjunction with any suitable grinder (such as ahammer mill, a ball mill, a rod mill, or a combination thereof, or thelike), such that at least a portion of the carbonaceous material isground, optionally in the presence of the hydrocarbonaceous liquidand/or the one or more catalysts or catalyst precursors and mixed toform a homogenous or heterogeneous slurry, as desired. In someembodiments, the mixer and/or grinder comprises a gas delivery systemfor providing an inert or a reducing atmosphere (such as, for example,hydrogen, nitrogen, helium, argon, syn-gas, or any combination ormixture thereof) during mixing and/or grinding of the carbonaceousmaterial, the hydrocarbonaceous liquid, and/or the catalyst or catalystprecursors. In some embodiments, the mixer and/or grinder are situatedupstream of the pretreatment system. In other embodiments, the mixerand/or grinder form a portion of the pretreatment system. Inembodiments, the catalyst precursor used in this process can be mixeddirectly to ground coal or other carbonaceous materials before feedinginto the reactor, or added into coal during coal solvent grinding. Thecatalyst can be dissolved and sprayed onto coal or impregnated onto coalby incipient wetness using methanol/ethanol or water asdissolving/wetting agent. The catalyst can also be dispersed or solublein the solvent that is then mixed with coal.

An embodiment of the invention is illustrated in FIG. 1. Coal feed 3,with at least 50 wt % of the coal particles having a mean particlediameter of less than 0.5 inches, is combined with catalytic material 5,comprising an active source of zinc and an active source of iron in amolar ratio of zinc to iron within the range of between 0.1/1 to 10/1,and the combination 1 is passed to preheat furnace 20 for heating to areaction temperature in the range of between 350° C. and 500° C. Theheated combination of coal and the catalytic material 23 leaving thepreheat furnace is then passed to reaction zone 30 for conversion of atleast a portion of the coal to liquid product 33.

Considering an exemplary process of the invention illustrated in FIG. 2,coal feed 103, with at least 50 wt % of the coal particles having a meanparticle diameter of less than 0.5 inches, is combined with catalyticmaterial 105, comprising an active source of zinc and an active sourceof iron in the molar ratio of zinc to iron within the range of between0.1/1 to 10/1, and the combination 101 is passed to pretreatment zone110 for maintaining the combination at a pretreatment temperature withinthe range of 100-350° C. and for a time of between 5 and 600 minutes.Following pretreatment, the combination 113 is passed to preheat furnace120 for heating to a reaction temperature in the range of between 350°C. and 500° C. The heated combination of coal and the catalytic material123 leaving the preheat furnace is then passed to reaction zone 130 forconversion of at least a portion of the coal to liquid product 133.

Considering an exemplary process of the invention illustrated in FIG. 3,coal feed 203, with at least 80 wt % of the coal particles having a meanparticle diameter in the range of 50 microns to 500 microns, is passedto pretreatment zone 210. In a particular exemplary process, coal issupplied to pretreatment zone as a powder. In another exemplary process,coal is supplied as a slurry in a hydrocarbonaceous liquid, such as acoal derived distillate fraction.

A catalytic material 205, comprising an active source of zinc and anactive source of iron in the molar ratio of zinc to iron within therange of between 3/1 and 1/3, is combined with the coal particles in thepretreatment zone. In an embodiment, the zinc is supplied to thepretreatment zone as an aqueous solution or slurry of a zinc salt suchas zinc nitrate, zinc chloride, zinc sulfate, zinc acetate, zincsulfide, zinc oxide or zinc carbonate. Iron is supplied to thepretreatment zone as an aqueous solution or slurry of an iron salt suchas iron nitrate, iron chloride, iron sulfate, iron acetate, ironsulfide, iron oxide or iron carbonate. In another embodiment, zinc andiron are added as organometallic compounds contained in a liquid such asa coal derived distillate fraction. Exemplary organometallic compoundsinclude zinc alkyl dithiocarbamate and ferrocene. An active source ofsulfur 207 is added to the pretreatment zone to supply a sulfur tocatalytic metal atomic ratio within the range of between 2/1 and 6/1.Hydrogen or a hydrogen containing gas 209 is further supplied to thepretreatment zone to maintain a pressure within the pretreatment zonewithin a range of between atmospheric pressure and 500 psig. In anotherembodiment, hydrogen or a hydrogen containing gas is supplied to thepretreatment zone to maintain a pressure within the pretreatment zonewithin a range of between 500 psig and 3500 psig. The materials in thepretreatment zone are maintained at a pretreatment temperature withinthe range of 180-220° C. and for a time of between 5 and 600 minutes.Following pretreatment, the combination 213 is passed to preheat furnace220 for heating to a reaction temperature in the range of between 350°C. and 500° C. The heated combination of coal and the catalytic material223 leaving the preheat furnace is then passed to reaction zone 230 forconversion of at least a portion of the coal to liquid product 233.

Considering an exemplary process of the invention illustrated in FIG. 4,coal feed 303, with at least 50 wt % of the coal particles having a meanparticle diameter of less than 0.5 inches is passed to pretreatment zone310. A catalytic material 307, comprising an active source of zinc and acatalytic material comprising an active source of iron 309 in the molarratio of zinc to iron within the range of between 0.1/1 to 10/1, arecombined with the coal particles in the pretreatment zone, and thecombination is maintained at a pretreatment temperature within the rangeof 100-350° C. and for a time of between 5 and 600 minutes. Followingpretreatment, the combination 313 is passed to preheat furnace 320 forheating to a reaction temperature in the range of between 350° C. and500° C. The heated combination of coal and the catalytic material 323leaving the preheat furnace is then passed to reaction zone 330 forconversion of at least a portion of the coal to liquid product 333.

Hydroconversion

The carbonaceous material is subjected to any suitable hydroconversionand/or liquefaction conditions to produce a product-enrichedhydrocarbonaceous material comprising any desired liquid and/or gaseousproducts. The carbonaceous material (such as coal) is introduced into atleast one hydroconversion zone wherein the pretreated carbonaceousmaterial encounters suitable temperature, pressure, and additives (suchas sulfur-containing compounds) to at least partially or substantiallyactivate the catalyst or catalyst precursor of the pretreatedcarbonaceous material, and generate liquid and/or gaseous products. Inone embodiment, for example, greater than about 50 wt. %, such as about55 wt. %, about 60 wt. %, about 65 wt. %, about 70 wt. %, about 75 wt.%, about 80 wt. %, about 85 wt. %, about 90 wt. %, about 95 wt. %, about96 wt. %, about 97 wt. %, about 98 wt. %, or even about 99 wt. % of thecatalyst or catalyst precursor of the pretreated carbonaceous materialbecomes active catalyst, such that it possesses and/or exhibitshydroconverting activity.

Suitable hydroconverting temperatures include, but are not limited to,temperatures greater than about 350° C., such as greater than about 375°C., about 400° C., about 425° C., about 450° C., about 475° C., about500° C. In some such embodiments, the step of hydroconverting the heatedmaterial is conducted at a temperature in the range of between 350° C.and 500° C. In some such embodiments, the heated material is reacted inthe hydroconversion step for a time of at least 10 minutes.

Suitable hydroconverting pressures include, but are not limited to,within the range of 300-5000 psig (such as within the range of about300-4800 psig, about 300-4600 psig, about 300-4400 psig, about 300-4200psig, about 400-4000 psig, about 500-3500 psig, 1000-3000 psig,1200-2800 psig, 1400-2600 psig, or even about 1500-2600 psig) of anysuitable gas such as a hydrogen containing gas (such as ahydrogen/methane mixture, or a hydrogen/carbon dioxide/water mixture)atmosphere and/or a syn-gas atmosphere. In one embodiment, in thisregard, the pretreated carbonaceous material is suitable for low orlower pressure hydroconversion (such as a hydroconversion pressure lessthan about 2000 psig, such as less than about 1800 psig, or even lessthan about 1600 psig). Specifically, for example, hydroconversion of thepretreated carbonaceous material can yield at least about 10% higher(such as at least about 20%, about 40%, about 60%, about 80%, about100%, about 150%, about 200%, about 300%, or even at least about 400%higher liquid product yield at a hydroconversion pressure less thanabout 2000 psig (such as less than about 1800 psig, or even less thanabout 1600 psig) than the same carbonaceous material that has not beenpretreated. In another embodiment, hydroconversion of the pretreatedcarbonaceous material consumes about 10% less (such as about 20%, about30%, about 40%, about 50%, about 60%, about 70%, about 80%, about 90%,or even about 100% less) hydrogen, as compared to the same carbonaceousmaterial that has not been pretreated.

In embodiments, the hydroconversion of the solid carbonaceous materialis accomplished by heating the solid carbonaceous material for a timesufficient to form a liquid product. In some such embodiments, the solidcarbonaceous material is heating in the presence of at least one activesource of zinc and at least one active source of a second metal. In somesuch embodiments, the solid carbonaceous material is heated at areaction temperature of greater than 350° C. and at a pressure in therange of 300 to 5000 psig. In some such embodiments, the solidcarbonaceous material is heated at a reaction temperature in the rangeof between 350° C. and 500° C. In some embodiments, the solidcarbonaceous material is heated for a time within the range of 5 minutesto 600 minutes.

In one embodiment, hydroconversion and/or liquefaction of thecarbonaceous material occurs in a single reactor. In another embodiment,hydroconversion and/or liquefaction of the carbonaceous material occursin two or more (such as a plurality) of zones or reactors forhydroconversion which may be arranged in any suitable manner (such as inparallel, or in series such that, for example, the temperature in eachreactor in series is progressively higher and/or there is a commensurateincrease in the hydrogen partial pressure in each downstream reactor).

Preferably, hydroconversion and/or liquefaction of the pretreatedcarbonaceous material occurs in a reactor or zone that is separateand/or distinct from the pretreatment reactor or zone.

In one embodiment, hydroconversion and/or liquefaction of thecarbonaceous material produces a liquid yield greater than about 50%,about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about85%, about 87%, about 90%, about 95%, or even greater than about 99%. Inan embodiment, pretreatment of the carbonaceous material results in aliquid yield that is at least about 10% higher (such as at least about15%, about 20%, about 25%, about 30%, about 35%, or even at least about40% higher) than the liquid product yield of a similar carbonaceousmaterial that is not pretreated prior to hydroconversion. In anotherembodiment, hydroconversion and/or liquefaction of the pretreatedcarbonaceous material produces a total conversion (such as of coal)greater than about 80%, about 85%, about 90%, about 95%, or even 99%.

In some embodiments, pretreatment of the carbonaceous material resultsin a total conversion (such as of coal) that is at least about 5% higher(such as at least about 10%, about 12%, about 14%, about 16%, about 18%,or even at least about 20% higher) than the conversion of a similarcarbonaceous material that is not pretreated prior to hydroconversion.In other embodiments, hydroconversion and/or liquefaction of thepretreated carbonaceous material produces less than about 10% (such asless than about 8%, about 6%, about 4%, about 3%, about 2%, or even lessthan about 1%) of C₁-C₃ gases.

Separation of Hydroconversion Products

The effluent from the hydroconversion zone can be fed into any suitableone or more separation zones. In one embodiment, the effluent is fedinto a first separation zone wherein lighter products such as gases,naptha, and distillate are removed via overhead lines. Such a firstseparation zone can be run at a substantially atmospheric pressure. Abottoms, or high boiling, fraction of the effluent from the firstseparation zone can optionally be recycled to the hydroconversionreaction zone. All or some of the remaining effluent of the firstseparation zone can be passed to a second separation zone wherein it isfractionated into a gas oil fraction and a bottoms fraction. The bottomsfraction of the second separation zone can be passed to a thirdseparation zone. A portion of the gas oil can be recycled to thehydroconversion zone. In this regard, any suitable high pressure, mediumpressure, and low pressure separators can be used in the context of thepresent invention.

Recovery of Catalyst or Catalyst Precursor

The one or more separation systems or zones can be followed by one ormore catalyst and/or metal recovery systems or zones in which at least aportion (such as one or more metals) of the catalyst and/or catalystprecursor is recovered from one or more portions or fractions of thehydroconverted carbonaceous material. In one embodiment, metal from ametal-containing catalyst and/or metal-containing catalyst precursor isrecovered in the recovery system from a solids fraction (such as aresidual solids fraction) of the hydroconverted carbonaceous materialthat was separated and/or collected in the separation system (and whichmay include ash).

The recovery system can be operated at any suitable temperature, such asat a temperature of about 1200-1900° C., such as about 1300-1800° C., oreven 1400-1700° C. In one embodiment, the recovery system provides anatmosphere of air that is suitable to cause spent catalysts (such asmolybdenum sulfides) to be oxidized and sublimated to Mo0₃, in the casewhere the metal is molybdenum, such as described in U.S. Pat. App. Ser.No. 60/015,096, filed Dec. 19, 2007, the contents of which areincorporated by reference in their entirety. The treated spent catalyst,catalyst precursor, and/or recovered metal can be collected and passedfrom the catalyst recovery zone to a catalyst or catalyst precursorpreparation zone.

Catalyst or Catalyst Precursor Preparation

The one or more recovery systems can be followed by one or more catalystor catalyst precursor preparation systems, in which at least a portionof the catalyst or catalyst precursor (such as metal of the catalystprecursor) recovered in the recovery system is reacted to form acatalyst or catalyst precursor (such as the same catalyst or catalystprecursor that was originally used to pretreat the carbonaceousmaterial).

In one embodiment, for example, a recovered metal of the catalyst orcatalyst precursor (such as MoO₃) is reacted with a sulfur compound(such as ammonium sulfide) to form ammonium tetrathiomolybdate catalystprecursor. The resulting formed catalyst or catalyst precursor can thenbe delivered, optionally in combination with new or fresh catalystprecursor, into the pretreatment system and/or the hydroconversionsystem.

Characterization of the Catalyst

In embodiments, a catalyst which is active for converting at least aportion of the solid carbonaceous material to a liquid product, havingthe formula(R^(p))_(i)(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))_(h)and having improved morphology and dispersion characteristics, can becharacterized using techniques known in the art, including elementalanalysis, Surface Area analysis (BET), Particle Size analysis (PSA),Powder X-ray Diffraction (PXRD), Scanning Electron Microscopy (SEM),Energy Dispersive X-ray Analysis (EDS), and other methods. In onemethod, electron microscopy is used to complement the x-ray diffractionstudy. In another method, the surface area of the catalyst is determinedusing the BET method. In yet another method, scanning tunnelingmicroscopy (STM) and density functional theory (DFT) can be used tocharacterize the catalyst.

The catalyst of the formula(R^(p))_(i)(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))^(h)is characterized as giving excellent conversion rates in the upgrades ofcoal depending on the configuration of the upgrade process and theconcentration of the catalyst used. In one embodiment, the slurrycatalyst provides conversion rates of at least 70% in one embodiment, atleast 75% in a second embodiment, at least 80% in a third embodiment,and at least 90% in a fourth embodiment. In one embodiment of a coalupgrade system employing the catalyst of the formula(R^(p))_(i)(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))^(h),at least 98 wt. % of coal feed is converted to lighter products. In asecond embodiment, at least 98.5% of coal feed is converted to lighterproducts. In a third embodiment, the conversion rate is at least 99%. Ina fourth embodiment, the conversion rate is at least 95%. In a fifthembodiment, the conversion rate is at least 80%. As used herein,conversion rate refers to the conversion of coal feedstock to less than1200° F. (650° C.) boiling point materials.

In one embodiment, the catalyst has a pore volume in the range of from0.05 to 5.0 ml/g as determined by nitrogen adsorption. In a secondembodiment, the pore volume is in the range of from 0.1 to 4.0 ml/g,such as from 0.1 to 3.0 ml/g or from 0.1 to 2.0 ml/g.

In embodiments, the catalyst has a surface area of at least 5 m²/g, orat least 10 m²/g, or at least 50 m²/g, or greater than 100 m²/g, orgreater than 200 m²/g, as determined via the B.E.T. method. Inembodiments, the catalyst is characterized by aggregates of crystallitesof 10 to 20 angstrom, for an overall surface area greater than 100 m²/g.

In embodiments, the catalyst has a particle size ranging from nanometerto micrometer (μm) size dimensions. Exemplary suspended catalystparticles have a median particle size of 0.0005 to 1000 microns, or amedian particle size of 0.001 to 500 microns, or a median particle sizeof 0.005 to 100 microns, or a median a particle size of 0.05 to 50microns. In embodiments, the catalyst in the form of a suspension thatis characterized by a median particle size of 30 nm to 6000 nm. Inembodiments, the catalyst has an average particle size in the range of0.3 to 20 μm.

In embodiments, the catalyst comprises catalyst particles of moleculardimensions and/or extremely small particles that are colloidal in size(i.e., less than 1 micrometer or less than 0.1 micrometer or in therange of 0.1 to 0.001 micrometer). In some embodiments, the catalyst isdispersed on the coal surface in 1 to 100 nanometer particles byimpregnation of the catalyst precursor on the coal. In some embodiments,the catalyst forms a slurry catalyst, in a hydrocarbon diluent, having“clusters” of the colloidal particles, with the clusters having anaverage particle size in the range of 1-100 micrometers.

As is further illustrated in the following examples, the systems andprocesses described herein can be used to achieve optimization andefficiency in the production of any desired proportions (or yieldpercentages) of liquid and/or gas products having a variety of desiredproperties. Specifically, a full range of hydroconversion products canbe accomplished under a variety of hydroconversion conditions (such asat low hydrogen pressure and/or with short duration) through selectionof any of a variety of combinations of hydrocarbonaceous liquid,catalysts and/or catalyst precursors, as well as pretreatment andhydroconversion conditions. In this manner, the systems and processoffers tremendous flexibility to a user in being able to achieve desiredhydroconversion products from any solid carbonaceous material using anyof a variety of different combinations of hydrocarbonaceous liquid,catalyst, and/or catalyst precursor, as well as pretreatment andhydroconversion conditions.

EXAMPLES Example 1

Run 1—A solution of a mixed catalyst precursor iron nitrate(Fe(NO₃)₃.9H₂O) and zinc nitrate (Zn(NO₃)₂.6H₂O) dissolved in methanolwas prepared. A sample of moisture-free coal feed (i.e. less than 1% byweight water) having a particle size of less than 100 mesh wasimpregnated to incipient wetness with the solution, at a solution tocoal weight ratio of 1 to 1, to yield an iron to coal loading on a dry,ash-free basis of 1% iron and a zinc to coal loading on a dry, ash-freebasis of 1 wt % zinc. The catalyst impregnated coal was then dried undernitrogen at 105° C. for up to 24 hr for to remove the methanol.

The dried catalyst impregnated coal was mixed with an FCC-type processoil (500° F.+cut) hydrocarbonaceous liquid, at a hydrocarbonaceousliquid to coal ratio of 1.6 to 1. Elemental sulfur was added to sulfidethe iron and zinc, at a sulfur to iron molar ratio of 2 to 1 and asulfur to zinc ratio of 2 to 1.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 430° C., and then held at 430° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia.

After 3 hours the reaction vessel containing the sulfided solvent andcoal mixture, hydrogen and any reaction products was quenched to roomtemperature. Product gases (CO, CO₂, C₁, C₂ and C₃) were vented througha wet test meter to determine the gas yield. Solids, primarilyunconverted coal, ash and catalyst sulfide were separated from liquidproducts (C₄ ⁺) by filtration. Coal conversion was determined asfollows:

Coal conversion=(solids recovered−(ash in coal+recovered catalyst))/coalfeed

By subtracting the solvent added at the beginning of the run, oil yieldwas determined based on coal (dry, ash-free basis). Product yields aretabulated as Run 1 in Table I.

Run 2—Example 1 was repeated using iron sulfate (FeSO₄.7H₂O) and zincnitrate (Zn(NO₃)₂.6H₂O) mixed catalyst precursor at an iron to coalloading on a dry, ash-free basis of 1 wt % iron, and a zinc to coalloading on a dry, ash-free basis of 1 wt % zinc. Elemental sulfur wasadded to sulfide the iron and zinc, at a sulfur to iron molar ratio of 2to 1 and a sulfur to zinc ratio of 2 to 1. Product yields are tabulatedas Run 2 in Table I.

Run 3—Example 1 was repeated using zinc nitrate (Zn(NO₃)₂.6H₂O) as aportion of the mixed catalyst precursor, to yield an zinc to coalloading on a dry, ash-free (dry, ash-free) basis of 1% zinc. Ferrocenewas further added into the solvent coal mixture at a iron to coalloading on a dry, ash-free basis of 3% iron.

Product yields are tabulated as Run 3 in Table I. The results set forthis Table II show excellent coal conversation and liquid yield for runs1, 2 and 3 of Example 1.

Detailed product distributions for runs 1, 2 and 3 in Table I areillustrative of distributions used to calculate the coal conversion. Theliquid product distribution was determined by subtracting the simulateddistillation result (or boiling curve) of the hydrocarbonaceous liquidfrom the simulated distillation result (or boiling curve) of the mixtureof hydrocarbonaceous liquid and liquid product.

Example 2

Run 4—Run 1 was repeated. Product yields tabulated for Run 4 in Table Iindicate excellent coal conversions and liquid yield for Run 4.

Example 3

Run 5—Run 1 was repeated using a iron nitrate (Fe(NO₃)₃.9H₂O) and zincnitrate (Zn(NO₃)₂.6H₂O) mixed catalyst precursor at an iron to coalloading on a dry, ash-free basis of 1 wt % iron, and a zinc to coalloading on a dry, ash-free basis of 1 wt % zinc. No elemental sulfur wasadded. Product yields tabulated for Run 5 in Table I indicate relativelypoor coal conversation and liquid yield.

Example 4

Run 6—Run 1 was repeated with iron sulfate (FeSO₄.7H₂O) dissolved inmethanol as the only catalyst precursor at an iron to coal loading on adry, ash-free basis of 1% iron. Elemental sulfur was added to thesolvent and coal mixture at a sulfur to iron molar ratio of 2 to 1 tosulfide the iron catalyst. Product yields tabulated as Run 6 in Table Iindicate moderate coal conversion and liquid yield.

Example 5

Run 7—Run 4 was repeated with zinc nitrate (Zn(NO₃)₂.6H₂O) dissolved inmethanol as the only catalyst precursor at a zinc to coal loading on adry, ash-free basis of 1% zinc. Elemental sulfur was added to thesolvent and coal mixture at a sulfur to zinc molar ratio of 2 to 1. Thereaction temperature was 430° C. rather than 440° C. Product yieldstabulated as Run 7 in Table I indicate poor coal conversion and poorliquid yield.

Example 6

Run 8—Iron nitrate (Fe(NO₃)₃.9H₂O) and zinc nitrate (Zn(NO₃)₂.6H₂O) weredissolved in de-ionized water. Coal was then dispersed into the aqueoussolution, which was then titrated drop-wide by base solution of NaOH.Following the titration, the mixture was aged at 40° C. for 5 hoursunder a flowing air purge. After aging, the mixture was centrifuged andtriple rinsed with a large quantity of water to remove excess base. Theresulting mixture was dried under nitrogen atmosphere at 105° C.

The reaction mixture was prepared with an FCC-type process oil (500°F.+cut) hydrocarbonaceous liquid, at a hydrocarbonaceous liquid to coalratio of 1.6 to 1. Elemental sulfur (sulfur to iron atomic ratio=2 to 1plus sulfur to zinc atomic ratio=2 to 1) was added to sulfide the activemetals in-situ.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 430° C., and then held at 430° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia. Product yields tabulatedfor Run 5 in Table I indicate relatively poor coal conversation andliquid yield. Product yields tabulated for Run 8 in Table I indicaterelatively poor coal conversation and liquid yield.

Run 9—Run 6 was repeated, but with sulfur being omitted from thecatalyst preparation. Product yields are tabulated as Run 9 in Table I.Product yields tabulated for runs 8 and 9 in Table I indicate a poorcoal conversion and liquid yield.

Example 7

Run 10—Run 8 was repeated by dissolving iron nitrate (Fe(NO₃)₃.9H₂O)alone in de-ionized water, with coal at an iron to coal loading on adry, ash-free coal basis of 1% iron. Product yields tabulated as Run 10in Table I indicate moderate coal conversion and liquid yield.

Example 8

Run 11—Iron sulfide (FeS) was dispersed in methanol and the dispersionmixed with coal, having a particle size of less than 100 mesh, at asolution to coal weight ratio of 1 to 1, to yield an iron to coalloading on a dry, ash-free (daf) basis of 1% iron. The mixture was thendried under nitrogen at 105° C. for up to 24 hr for to remove themethanol.

The dried catalyst impregnated coal was mixed with an FCC-type processoil (500° F.+cut) hydrocarbonaceious liquid, at a hydrocarbonaceousliquid to coal ratio of 1.6 to 1. Elemental sulfur was added to thesolvent and coal mixture at a sulfur to iron molar ratio of 2 to 1 tosulfide the iron catalyst.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 440° C., and then held at 440° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia. Product yields aretabulated as Run 11 in Table I.

Run 12—Run 11 was repeated using a mixture of iron sulfide and zincsulfide at a iron to coal loading of 0.56% iron and a zinc to coalloading of 1% zinc. The results set forth in Table I indicate poor coalconversion and liquid yield for both Run 11 and Run 12.

Example 9

Run 13—A sample of moisture-free coal feed (i.e. less than 1% by weightwater) having a particle size of less than 100 mesh was mixed with anFCC-type process oil (500° F.+cut) as solvent, at a solvent to coalratio of 1.6 to 1. Iron (III) dimethyldithiocarbamate and zincdiethyldithiocarbamante was blended in the solvent coal mixture to yieldan iron to coal loading on a dry, ash-free (daf) basis of 1% iron and azinc to coal loading on a dry, ash-free (daf) basis of 1% zinc. Noadditional sulfur was added.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 430° C., and then held at 430° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia.

The results set forth in Table I show excellent coal conversions andliquid yield for Run 13.

Example 10

Run 14—A solution of the mixed catalyst precursor iron nitrate(Fe(NO₃)₃.9H₂O) and zinc nitrate (Zn(NO₃)₂.6H₂O) dissolved in methanolwas prepared. A portion of coal representing 20% of the total coalsample (moisture-free coal feed (i.e. less than 1% by weight water)having a particle size of less than 100 mesh) was selected. The coalportion was impregnated to incipient wetness with the solution, at asolution to coal weight ratio of 1 to 1. The catalyst impregnated coalportion was then dried under nitrogen at 105° C. for up to 24 hr for toremove the methanol. The remaining 80% of the total coal sample wasmixed with the dried portion, to yield an iron to coal loading on a dry,ash-free (daf) basis of 1% iron and a zinc to coal loading on a dry,ash-free (daf) basis of 1% zinc.

The dried coal sample was mixed with an FCC-type process oil (500°F.+cut) as solvent, at a solvent to coal ratio of 1.6 to 1. Elementalsulfur was added to sulfide the iron and zinc, at a sulfur to iron molarratio of 2 to 1 and a sulfur to zinc ratio of 2 to 1.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 440° C., and then held at 440° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia.

Product yields set forth in Table I indicate good coal conversion andliquid yield.

Example 11

Run 15—Moisture-free coal feed (i.e. less than 1% by weight water)having a particle size of less than 100 mesh was dispersed in 1% dioctylsulfosaccinate sodium aqueous solution, following by addition of ironnitrate (Fe(NO3)3.9H2O) and zinc nitrate (Zn(NO3)2.6H2O) catalystprecursors, to yield an iron to coal loading on a dry, ash-free (daf)basis of 1% iron and a zinc to coal loading on a dry, ash-free (daf)basis of 1% zinc. The catalyst impregnated coal portion was then driedunder nitrogen at 105° C. for up to 24 hr for to remove the water.

The dried coal sample was mixed with an FCC-type process oil (500°F.+cut) as solvent, at a solvent to coal ratio of 1.6 to 1. Elementalsulfur was added to sulfide the iron and zinc, at a sulfur to iron molarratio of 2 to 1 and a sulfur to zinc ratio of 2 to 1.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 440° C., and then held at 440° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia.

Product yields set forth in Table I indicate good coal conversion andliquid yield.

Example 12

Run 16—A solution of a mixed catalyst precursor iron nitrate(Fe(NO₃)₃.9H₂O) and zinc nitrate (Zn(NO₃)₂.6H₂O) dissolved in de-ionizedwater was prepared. A sample of moisture-free coal feed (i.e. less than1% by weight water) having a particle size of less than 100 mesh wasdispersed in the aqueous solution, which was treated by NH₄OH drop-wise.Following the titration, the mixture was aged at 40° C. for 5 hours inflowing air. After aging, the mixture was centrifuged and triple rinsedwith a large quantity of water to remove excess base. The resultantmixture was dried under nitrogen atmosphere at 105° C.

The dried catalyst impregnated coal was mixed with an FCC-type processoil (500° F.+cut) as solvent, at a solvent to coal ratio of 1.6 to 1.Elemental sulfur was added to sulfide the iron and zinc, at a sulfur toiron molar ratio of 2 to 1 and a sulfur to zinc ratio of 2 to 1.

The mixture was then heated quickly in a vessel to 200° C., and held at200° C. for 2 hours, while the hydrogen partial pressure within thevessel increased from about 100 psia to about 1000 psia. The mixture wasthen further heated to 440° C., and then held at 440° C. for 3 hoursunder a hydrogen partial pressure of 2500 psia.

Product yields set forth in Table I indicate good coal conversion andliquid yield.

Example 13

Run 17—Run 1 was repeated using ammonium sulfate ((NH₄)₂SO₄) andammonium nitrate (NH₄NO₃) dissolved in methanol in place of a catalystprecursor at an NH₃ to coal loading on a dry, ash-free basis of 1 wt %NH₃ from ammonium sulfate, and an NH₃ to coal loading on a dry, ash-freebasis of 1 wt % NH₃ from ammonium nitrate. Elemental sulfur was added tothe solvent and coal mixture to provide 1.14% by weight of sulfur on thecoal. The results set forth in Table I indicate that this comparativerun without catalyst had poor coal conversion and low liquid yield.

TABLE I Liquid Coal Gas Example Run Yield (%) Conversion (%) Yield (%) 11 78.0 97.5 14.4 1 2 77.4 97.2 18.3 1 3 77.9 97.4 14.5 2 4 73.5 96.414.0 3 5 57.2 93.5 15.0 4 6 66.6 90.7 19.1 5 7 58.0 90.2 17.5 6 8 55.093.0 — 6 9 56.2 92.3 20.0 7 10 62.5 94.4 19.6 8 11 47.6 92.3 20.9 8 1244.7 91.1 20.0 9 13 72.7 96.0 14.6 10 14 67.5 94.3 18.5 11 15 73.8 97.014.9 12 16 71.5 93.9 12.6 13 17 33.7 68.0 17.6

TABLE II Run 1 2 3 Coal conversion, (%) dry, 97.2 97.5 97.4 ash-freebasis Yield (% dry, ash-free coal) C₁-C₃ 9.2 5.7 6.8 Total gas 18.3 14.414.5 C4-350° F. 4.8 4.6 6.4 350-650° F. 40.4 40.5 35.7 650-850° F. 24.624.7 27.8 C4-850° F. 69.8 69.8 69.9 850-1000° F. 5.9 6.2 6.4 >1000° F.1.7 2.0 1.6 H₂O 8.2 11.8 9.0 H2 consumption 6.7 6.7 4.0 C4-850° F.liquid bbl/ton dry, 4.9 4.9 4.9 ash-free coal H₂ consumption scf/bbl5432 5432 3239 Hexane insoluble (% dry, 21.2 19.4 19.5 ash-free coal)MCR (% dry, ash-free coal) 4.2 3.0 3.4 Detailed carbon elemental massbalance C feed from coal 26.40 26.76 26.51 C in the product liquid 22.0322.16 22.33 C in the product gas 2.71 3.35 2.4 C in the product solid1.47 1.32 1.29 C out 26.21 26.83 26.01

1. A process for converting solid carbonaceous material to a liquidproduct, comprising maintaining a solid carbonaceous material in thepresence of at least one active source of zinc at a reaction temperatureof greater than 350° C. and at a pressure in the range of 300 to 5000psig for a time sufficient to form a liquid product.
 2. A process forconverting solid carbonaceous material to a liquid product, comprisingmaintaining a solid carbonaceous material in the presence of at leastone active source of zinc and at least one active source of a secondmetal at a reaction temperature of greater than 350° C. and at apressure in the range of 300 to 5000 psig for a time sufficient to forma liquid product.
 3. The process of claim 2, the process comprising: a)preparing a combination of the solid carbonaceous material, at least onehydrocarbonaceous liquid, at least one active source of zinc and atleast one active source of the second metal; and b) passing thecombination to a hydroconversion reaction zone and maintaining the solidcarbonaceous material at a reaction temperature of greater than 350° C.and at a pressure in the range of 300 to 5000 psig for a time sufficientto convert at least a portion of the solid carbonaceous material to aliquid product boiling in the temperature range of C₅ to 650° C.
 4. Theprocess of claim 3, wherein the step of preparing the combinationcomprises: a) preparing a mixture comprising at least one active sourceof zinc and at least one active source of a second metal; b) combiningthe mixture with coal to form catalyst-containing coal particles; and c)providing a hydrocarbonaceous liquid to the catalyst-containing coalparticles to prepare the combination.
 5. The process of claim 4, furthercomprising drying the catalyst-containing coal particles prior to thestep of passing the combination to the hydroconversion reaction zone. 6.The process of claim 4, wherein the mixture further comprises asurfactant.
 7. The process of claim 3, further supplying an activesource of sulfur to the combination.
 8. The process of claim 7, whereinthe active source of sulfur is supplied at an atomic ratio of sulfur tometal within the range of between 0.1 to 1 and 10 to
 1. 9. The processof claim 3, further comprising supplying hydrogen or hydrogen-containinggas to the hydroconversion reaction zone.
 10. The process of claim 3,further comprising pretreating the combination at a pretreatmenttemperature within the range of 100-350° C. and for a time of between 5and 600 minutes prior to passing the combination to the hydroconversionreaction zone.
 11. The process of claim 10, further comprisingpretreating the combination in the presence of an active source ofsulfur.
 12. The process of claim 10, further comprising pretreating thecombination in the presence of hydrogen or a hydrogen-containing gas.13. The process of claim 2, wherein the second metal is selected fromthe group consisting of iron, molybdenum, nickel, manganese, vanadium,tungsten, cobalt, copper, titanium, chromium and tin.
 14. The process ofclaim 2, wherein the second metal is iron.
 15. The process of claim 2,wherein the second metal is copper.
 16. The process of claim 2, whereinthe zinc is present in an amount of 10 ppm to 10 wt %, based on dry, ashfree coal.
 17. The process of claim 2, wherein the second metal ispresent in an amount of 10 ppm to 10 wt %, based on dry, ash free coal.18. The process of claim 2, wherein zinc and the second metal arepresent in a molar ratio within the range of between 0.1 to 1 and 10to
 1. 19. The process of claim 1, further comprising maintaining thesolid carbonaceous material in the presence of at least one activesource of sulfur.
 20. The process of claim 1, further comprisingmaintaining the solid carbonaceous material in the presence of hydrogenor a hydrogen containing gas.
 21. The process of claim 3, furthercomprising converting at least 25% by weight of the solid carbonaceousmaterial to a liquid product boiling in the temperature range of C₅ to650° C.
 22. The process of claim 22, further comprising converting inthe range of 30% to 99% by weight of the solid carbonaceous material tothe liquid product.
 23. The process of claim 3, further comprisingmaintaining the solid carbonaceous material at a reaction temperature inthe range of between 350° C. and 800° C.
 24. The process of claim 2,wherein the active source of zinc and the active source of the secondmetal form a catalyst composition having a formula:(R^(p))_(i)(M^(t))_(a)(L^(u))_(b)(S^(v))_(d)(C^(w))_(e)(H^(x))_(f)(O^(y))_(g)(N^(z))^(h),wherein R is optional, R is at least a lanthanoid element metal or analkaline earth metal; M is zinc; L is at least a “d” block element metaldifferent from the “d” block element metal M;0<=i<=1;0<b/a=<5,0.5(a+b)<=d<=5(a+b),0<e<=11(a+b),0<f<=7(a+b),0<g<=5(a+b),0<h<=2(a+b), p, t, u, v, w, x, y, z, each representing total charge foreach of: M, L, S, C, H, O and N, respectively, whereinpi+ta+ub+vd+we+xf+yg+zh=0, S=sulfur, C=carbon, H=hydrogen, O=oxygen andN=nitrogen.
 25. The process of claim 24, wherein L is selected from thegroup consisting of iron, molybdenum, nickel, manganese, vanadium,tungsten, cobalt, copper, titanium, chromium, platinum, palladium,cerium, zirconium and tin.
 26. The process of claim 25, wherein L isiron.
 27. The process of claim 25, wherein L is copper.